Amides of acetoacetic acid and process for their preparation



Patented at. 22. 1949 UNITED STATES 1 PATENT OFFICE AMIDES F ACETOACETICACID AND PROCESS FOR THEIR PREPARATION John R. Caldwell, Kingsport,Tenn., minor to Eastman Kodak Company, Rochester, N. Y., a corporationof New Jersey No Drawing. Application June 21, 1946,

Serial No. 678,353

'1 Claims. 1

(Cl. zen-404.5)

2 ience, it is preferred to employ diketene as the source of theacetoacetyl radical CH3COCH:CO.

Diketene is derived from the polymerization of two molecules of keteneand has the structure l, Diketene reacts with amines according to theill tics and for the vinyl resins. The invention further provides newand improved conditioning agents for the treatment of yarns and fabrics.Many of the compounds of the invention are oil soluble and may be addedto lubricating oils and greases in order to improve the film strengthand adhesion to metals. The new compounds are also valuable as surfaceactive agents and may be employed as emulsifiers and detergents. Otherobjects will appear hereinafter.

In accordance with the invention these and other objects are attained bycondensing acetoacetic acid or a compound in which the acetoacetylradical is readily available with a substituted aliphatic amine orpolyamine to produce compounds having the general structure cmcoomcm-Nwherein R1 and R1 each may be a hydrocarbon radical containing 8 to 24carbon atoms which may be interrupted by one or more nitrogen atoms inthechain, and which radical may also con tain amide linkages. Either,but not both, R1. or R2 may also be a hydrogen atom when the other hasthe above stated values.

R1 and R2, for example, may include the hydrogen radicals CaH17-,C10Ha1-,

CaHuCHtCH (CH2) 8- C1aHar--, etc.; or may include such radicals, in

which an amide group interrupts the carbon chain, as C2H4NHCOC6H13,

equation:

R1 RI 0111:0435, HN cmooomcoN =O R1 Ra wherein R1 and R: have thesignificance described above.

The compounds of the invention are readily prepared by reactions of thefollowing types:

(a) Diketene is treated with a long chain alkylamine as'represented bythe equation:

CH:=C-CH1 NHz-CaHn =0 QHy-G0CHg-GONHC5B11 (b) A fatty acid is condensedwith a polyamine to produce a mixed amino-amide compound;

This product is then treated with diketene to form the acetoaceticderivative Fatty acids that may be employed in the process of theinvention include oleic, lauric, stearic, palmitic, ricinoleic,pelargonic, capric and arachidic acid. Also the napthenic acids derivedfrom pctroleum and containing 8 or more carbon atoms are advantageouslyadapted to the invention.

The diketene is reacted with the long chain alkylamine preferably in thepresence of an inert diluent such as ethylene dichloride, dioxane andtoluene and so forth, to aid in controlling the rate of reaction sincethe reaction is a vigorous exothermic reaction. The solution is stirredand the temperature is maintained by suitable cooling apparatus below C.and preferably in most instances in the range of 45-50" C. or below. Atthe conclusion of the reaction the diluent is distilled from theproduct.

If it is desired to form the alkylamine, the fatty acid and the amineselected may be heated in an esteriflcation apparatus employing asuitable water entrainer such as toluene and a suitable catalyst for thereaction such as toluene sulfonic acid. The heating may be conducted atapproximately 120 C. until substantial amounts of water are formed. Thissolution now containing alkylamines' may then be cooled within the rangeof 40-50 C. and diketene may be addedwhile the solution is stirred. Atthe conclusion- 0f the vigorous exothermic reaction the tolune'may beevaporated oil? under vacuum and the'product, and acetoacetamide,remains as the residue.

The invention is furtherdescribed in the following examples: 1

Example I Oleyl amine (octadecenylamine) (265 g. or 1.0 mol.) isdissolved in 500 cc. of ethylene dichloride. The solution is stirred andthe temperature is maintained at 45-50" C. while 84 g. (1 mol.) ofdiketene is slowly added. A vigorous exothermic reaction takes place.The ethylene dichloride is evaporated to leave a soft, waxy residue thatis N-acetoacetyl oleyl amine, having the structure CH3COCH2CONHC1aH35.The product is soluble in many organic solvents and is compatible withmany types of cellulose esters and vinyl resins. It has a soft, waxytexture and is valuable as a textile treating agent. When applied toyarns and fabrics the N-acetoacetyl oleyl amine imparts a soft, smoothhand and also acts as an anti-static agent.

' Example II 103 g. of diethylene triamine and 420 g. oleic acid wereheated at 120 C. in an esterification apparatus. using toluene as awater entrainer and toluene sulfonic acid as a catalyst. Heating -wascontinued until 28 to 30 cc. of water was eliminated. The productconsists primarily of V a mixture of amine-amides having the structureThese products are individually soluble in mineral oil and may be addedto lubricating oils and greases to increase the film strength andimprove adhesion to metals.

The mixture of acetoacetamides is especially valuable as a conditioningagent for textile yarns and fabrics. When applied to cellulose esterfilaments in spinning or twisting it imparts a soft, smooth hand andgreatly reduces the tendency toward static electrification.v

Example III Stearic acid and ethylenediamin'e are condensed by knownmethods to give the half-amide having the structure One mol of thehalf-amide i dissolved in dioxane and stirred at 50-60 C. while one molof diketene 4 is slowly added. The dioxane is evaporated in vacuum toleave a hard wax, melting at about 8090 C. and having the structure alsoadvantageously employed as plasticizers for amide having the structure:

cellulose ethers as represented by ethyl cellulose and benzyl cellulose,and for many types of vinyl resins including polyvinyl acetate,polyvinyl acetate-chloride etc.

The acetoacetic amide compounds containing the higher fatty acids thealkyl radicals of which have carbon atoms from C12 to C20 andparticularly stearic and oleic radicals are useful as textile finishingagents These compounds impart a soft, smooth hand to yarns and fabricsand reduce the tendency toward static electrification.

The acetoacetic amides of the invention may be added to lubricating oilsand greases to improve film strength and adhesion to metals or may beemployed as emulsifiers, detergents and surface active agents.

I claim:

1. The process of producing acetoacetyl amides which comprisescondensing diketene with a compound selected from the group consistingof those compounds which are represented by the following generalformulas:

the reaction mixture at a temperature of from 40 to 60 C.

3. The process of producing an acetoacetyl which comprises reactingdiketene with-a compound having the structure:

4. The process of producing an acetoacetyl wherein R1 represents analkyl radical containamide having the structure: in: from 8 to 24 carbonatoms. g g g o...NH c:H N c:H -NHcoc K 7. A chemical compound comprisingan aceto- O on) o OH acetyl amide having the structure:

5 which comprises reacting diketene with a. comcmooon'co NH N NH 00cmpound having the structure: 00310003 CflH.c0-NH-C,H.NH-c,m-NH-c0&1m JOHNR. CALDWELL. 5. The process of producing an acetoacetyi REFERENCES m t10 amide having the structure' The foliowin ref rences are of record inthe C11HasCONHCzH4-NH-COCH:COCI'11 e of this f comprises reactingdlketene 8. com- UNI'I'ED pound having the structure: 15 Numb N Due r8mg WHMCONHQHPNH" 2101,2332 Conquest Dec. v, 193': 6. The acetoacetylamides which are repre- 2,126,560 Kyridea Aug. 9, 1938 sented by thefollowing general formulas: 2,152,132 Boese Mar. 23, 1939 2,268,395Henke Dec. 3 1941 2,306,765 Stiller Dec. 29, 1943 and 2,345,632 Robinsonet a1. Apr. 4, 1944 CHaCOCH2CONHCaH4-NH--CzH4-NHCOR1 OTHER REFERENCESand 'Boese: Industrial and Eng. Chemistry (Jan moomr- -om-u-omemmom1940),vo1.32,'pa:es 16-22 oomooom

